This invention relates to a method for preventing the ignition of molten magnesium by contacting the molten magnesium with a gaseous mixture comprising a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof. This invention also relates to molten magnesium and solid magnesium comprising a film formed on a surface of the magnesium. This film is comprised of a reaction product of molten magnesium and a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof. The solid magnesium may be in the form of ignots or castings. The invention also relates to extinguishing a fire on the surface of magnesium by contacting the surface with the gaseous mixture described above.
Molded parts made of magnesium (or its alloys) are finding increasing use as components in the automotive and aerospace industries. These parts are typically manufactured in a foundry, where the magnesium is heated to a molten state in a crucible to a temperature as high as 1400xc2x0 F. (760xc2x0 C.), and the resulting molten magnesium is poured into molds or dies to form ingots or castings. During this casting process, protection of the magnesium from atmospheric air is essential to prevent a spontaneous exothermic reaction from occurring between the reactive metal and the oxygen in the air. Protection from air is also necessary to minimize the propensity of reactive magnesium vapors to sublime from the molten metal bath to cooler portions of a casting apparatus. In either situation, an extremely hot magnesium fire can result within a few seconds of air exposure, causing extensive property damage and, most tragically, serious injury to and devastating loss of human life.
Various methods have been investigated to minimize the exposure of molten magnesium to air. See J. W. Fruehling et al., Transactions of the American Foundry Society, Proceeding of the 73rd Annual Meeting, May 5-9, 1969, 77 (1969). The two most viable methods for effectively separating molten magnesium from air are the use of salt fluxes and the use of cover gases (sometimes referred to as xe2x80x9cprotective atmospheresxe2x80x9d). A salt flux is fluid at the magnesium melt temperature and it effectively forms a thin impervious film on the surface of the magnesium, thus preventing the magnesium from reacting with oxygen in the air. However, the use of salt fluxes presents several disadvantages. First, the flux film itself can oxidize in the atmosphere to harden into a thick oxychloride deposit, which is easily cracked to expose molten magnesium to the atmosphere. Second, the salt fluxes are typically hygroscopic and, as such, can form salt inclusions in the metal surface which can lead to corrosion. Third, fumes and dust particles from fluxes can cause serious corrosion problems to ferrous metals in the foundry. Fourth, salt sludge can form in the bottom of the crucible. Fifth, and not least, removal of such fluxes from the surface of cast magnesium parts can be difficult.
As a result, there has been a shift from using salt fluxes to using cover gases to inert molten magnesium. Cover gases can be described as one of two types: inert cover gases and reactive cover gases. Inert cover gases can be non-reactive (e.g., argon or helium) or slowly reactive (e.g., nitrogen, which reacts slowly with molten magnesium to form Mg3N2). For inert cover gases to be effective, air must be essentially excluded to minimize the possibility of metal ignition, i.e., the system must be essentially closed. To utilize such a closed system, workers either have to be equipped with a cumbersome self-contained breathing apparatus or they have to be located outside of the dimensions of the processing area (e.g., by using remote control). Another limitation of inert cover gases is that they are incapable of preventing molten metal from subliming.
Reactive cover gases are gases used at low concentration in a carrier gas, normally ambient air, that react with the molten magnesium at its surface to produce a nearly invisible, thermodynamically stable film. By forming such a tight film, the aerial oxygen is effectively separated from the surface of the molten magnesium, thus preventing metal ignition and minimizing metal sublimation.
The use of various reactive cover gases to protect molten magnesium from ignition has been investigated as early as the late 1920s. An atmosphere containing CO2 is innocuous and economical yet forms a protective film on a magnesium surface which can prevent ignition for over 1 hour at 650xc2x0 C. However, the CO2-based films formed are dull in appearance and unstable, especially in the presence of high levels of air, and consequently offer little protection for the magnesium surface from ambient oxygen. In effect, the CO2 behaves more like an inert cover gas than a reactive cover gas.
SO2 has been investigated in the past as a reactive cover gas, as SO2 reacts with molten magnesium to form a thin, nearly invisible film of magnesium oxysulfides. SO2 is low in cost and is effective at levels of less than 1% in air in protecting molten magnesium from ignition. However, SO2 is very toxic and consequently requires significant measures to protect workers from exposure (permissible exposure levels are only 2 ppm by volume or 5 mg/m3 by volume). Another problem with SO2 is its reactivity with water in humid air to produce very corrosive acids (H2SO4 and H2SO3). These acids can attack unprotected workers and casting equipment, and they also contribute significantly to acid rain pollution when vented out of the foundry. SO2 also has a tendency to form reactive deposits with magnesium which produce metal eruptions from the furnace (especially when SO2 concentrations in the air are allowed to drift too high). Though SO2 has been used commercially on a large scale for the casting of magnesium alloys, these drawbacks have led some manufacturers to ban its use.
Fluorine-containing reactive cover gases provide an inert atmosphere which is normally very stable to chemical and thermal breakdown. However, such normally stable gases will decompose upon contact with a molten magnesium surface to form a thin, thermodynamically stable magnesium oxyfluoride protective film. U.S. Pat. No. 1,972,317 (Reimers et. al.) describes the use of fluorine-containing compounds which boil, sublime or decompose at temperatures below about 750xc2x0 C. to produce a fluorine-containing atmosphere which inhibits the oxidation of molten magnesium. Suitable compounds listed include gases, liquids or solids such as BF3, NF3, SiF4, PF5, SF6, SO2F2, (CClF2)2, HF, NH4F and NH4PF6. The use of BF3, SF6, CF4 and (CClF2)2 as fluorine-containing reactive cover gases is disclosed in J. W. Fruehling et al., described supra.
Each of these fluorine-containing compounds has one or more deficiencies. Though used commercially and effectively at lower levels than SO2, BF3 is toxic and corrosive and can be potentially explosive with molten magnesium. NF3, SiF4, PF5, SO2F2 and HF are also toxic and corrosive. NH4F and NH4PF6 are solids which sublime upon heating to form toxic and corrosive vapors. CF4 has a very long atmospheric lifetime. (CClF2)2, a chlorofluorocarbon, has a very high ozone depletion potential (ODP). The ODP of a compound is usually defined as the total steady-state ozone destruction, vertically integrated over the stratosphere, resulting from the unit mass emission of that compound relative to that for a unit mass emission of CFC-11 (CCl3F). See Seinfeld, J. H. and S. N. Pandis, Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley and Sons, Inc., New York, (1998). Currently, there are efforts underway to phase out the production of substances that have high ODPs, including chlorofluorocarbons and HCFCs, in accordance with the Montreal Protocol. UNEP (United Nations Environment Programme), Montreal Protocol on Substances that Deplete the Ozone Layer and its attendant amendments, Nairobi, Kenya, (1987).
Until recently, SF6 was considered the optimum reactive cover gas for magnesium. SF6 is effective yet safe (essentially inert, odorless, low in toxicity, nonflammable and not corrosive to equipment). It can be used effectively at low concentrations either in air ( less than 1%) or in CO2 to form a very thin film of magnesium oxyfluorides and oxysulfides on the surface of molten magnesium. This magnesium oxyfluoride/oxysulfide film is far superior at protecting the magnesium from a vigorous exothermic oxidation reaction than is the magnesium oxide film inherently present on the metal surface. The magnesium oxysulfide/oxyfluoride film is sufficiently thin (i.e., nearly invisible to the naked eye) that the metal surface appears to be metallic. This superior protection is believed to result from the greater thermodynamic stability of a magnesium oxysulfide and/or magnesium oxyfluoride film as compared to the stability of a thick porous magnesium oxide, sulfide or fluoride film.
In a typical molten magnesium process employing a reactive cover gas, only a small portion of the gas passed over the molten magnesium is actually consumed to form that film, with the remaining gas being exhausted to the atmosphere. Efforts to capture and recycle the excess SF6 are difficult and expensive due to its very low concentrations in the high volumes of exhaust stream. Efficient thermal oxidizing equipment would be required to remove the SF6 from the exhaust stream, adding significantly to production costs. Product costs can also be considerable, as SF6 is the most expensive commercially used reactive cover gas.
However, perhaps the greatest concern with SF6 is its very significant global warming potential (3200 year atmospheric lifetime, and about 22,200 times the global warming potential of carbon dioxide). At the December 1997 Kyoto Summit in Japan, representatives from 160 countries drafted a legally binding agreement containing limits for greenhouse gas emissions. The agreement covers six gases, including SF6, and includes a commitment to lower the total emissions of these gases by the year 2010 to levels 5.2% below their total emissions in 1990. UNEP (United Nations Environment Programme), Kyoto Protocol to the United Nations Framework Convention on Climate Change, Nairobi, Kenya, 1997.
As no new replacement for SF6 is yet commercially available, efforts are underway to reinvigorate SO2, as SO2 has essentially no global warming potential (despite its other considerable drawbacks). See H. Gjestland, P. Bakke, H. Westengen, and D. Magers, Gas protection of molten magnesium alloys: SO2 as a replacement for SF6. Presented at conference on Metallurgie du Magnesium et Recherche d""Allegement dans Ixe2x80x3Industrie des Transports, International Magnesium Association (IMA) and Pole de Recherche et de Devleoppment Industriel du Magnesium (PREDIMAG) Clermond-Ferrand, France, October 1996.
The data in TABLE 1 summarize selected safety and environmental limitations of compounds currently known to be useful in the protection of molten magnesium. Numbers followed by an asterisk (*) are particularly problematic with regard to safety and/or environmental effects.
As each of these compounds presents either a significant safety or an environmental concern, the search continues to identify new reactive cover gases for protecting molten magnesium which are simultaneously effective, safe, environmentally acceptable, and cost-effective.
This invention relates to a method for treating molten magnesium to protect the magnesium from reacting with oxygen in air. The method comprises providing molten magnesium and exposing the magnesium to a gaseous mixture comprising a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof.
The gaseous mixture may further comprise a carrier gas. The carrier gas may be selected from the group consisting of air, carbon dioxide, argon, nitrogen and mixtures thereof.
This invention also relates to a method for protecting molten magnesium from reacting with oxygen in air. In this method the exposed surface of molten magnesium is exposed to or contacted with a gaseous mixture comprising a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof. The gaseous mixture can react with the molten magnesium at its exposed surface to produce a nearly invisible, thermodynamically stable film. By forming this film, the oxygen in air can be effectively separated from the surface of the molten magnesium and thus can prevent metal ignition and can minimize metal sublimation.
This invention also relates to molten magnesium protected from reacting with oxygen in air in accordance with the method of the present invention.
In addition, this invention relates to molten magnesium wherein a protective film is formed on a surface of the magnesium. This film is formed by a reaction of the magnesium with a gaseous mixture comprising a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones and mixtures thereof. This film can be nearly invisible and thermodynamically stable and can effectively separate oxygen in air from the surface of the magnesium and thus can prevent metal ignition and can minimize metal sublimation.
In another embodiment, this invention relates to solid magnesium comprising a film formed on a surface of the magnesium. This film is comprised of a reaction product of molten magnesium and a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof. This solid magnesium may be in the form of ignots or castings.
In yet another embodiment, this invention relates to a method for extinguishing a fire on the surface of magnesium comprising contacting a gaseous mixture comprising a fluorocarbon selected from the group consisting of perfluoroketones, hydrofluoroketones, and mixtures thereof, with said surface of said magnesium.
In this application, xe2x80x9cmagnesiumxe2x80x9d means magnesium and all alloys formed therefrom.
One advantage of the present invention over the known art is that the Global Warming Potentials of perfluoroketones and hydrofluoroketones are quite low. Therefore, the present inventive process is more environmentally friendly.
Fluorocarbons of the present invention include perfluoroketones (PFKs), and hydrofluoroketones (HFKs) which incorporate limited amounts of hydrogen in their structures. These fluorocarbons can be effective as reactive cover gases to protect reactive molten reactive metals such as molten magnesium from ignition. As is the case with known fluorine-containing reactive cover gases, these fluorocarbons can react with the molten metal surface to produce a protective surface film, thus preventing ignition of the molten metal.
For the protection of molten magnesium from ignition, fluorocarbons of the present invention are desirable alternatives to the most commonly used cover gas currently, SF6. The fluorocarbons of the present invention are low GWP fluorocarbon alternatives to SF6, i.e., the fluorocarbons of the present invention have measurably lower global warming potential relative to SF6 (i.e., significantly less than 22,200) and are not significantly worse in atmospheric lifetime, ozone depletion potential, or toxicity properties.
Perfluorinated ketones (PFKs) useful in the present invention include ketones which are fully fluorinated, i.e., all of the hydrogen atoms in the carbon backbone have been replaced with fluorine atoms. The carbon backbone can be linear, branched, or cyclic, or combinations thereof, and will preferably have about 5 to about 9 carbon atoms. Representative examples of perfluorinated ketone compounds suitable for use in the processes and compositions of the invention include CF3CF2C(O)CF(CF3)2, (CF3)2CFC(O)CF(CF3)2, CF3(CF2)2C(O)CF(CF3)2, CF3(CF2)3C(O)CF(CF3)2, CF3(CF2)5C(O)CF3, CF3CF2C(O)CF2CF2CF3, CF3C(O)CF(CF3)2, perfluorocyclohexanone, and mixtures thereof. In addition to demonstrating reactive cover gas performance, perfluorinated ketones can offer additional important benefits in safety of use and in environmental properties. For example, CF3CF2C(O)CF(CF3)2 has low acute toxicity, based on short-term inhalation tests with mice exposed for four hours at a concentration of 100,000 ppm in air. Also based on photolysis studies at 300 nm CF3CF2C(O)CF(CF3)2 has an estimated atmospheric lifetime of 5 days. Other perfluorinated ketones show similar absorbances and thus are expected to have similar atmospheric lifetimes. As a result of their rapid degradation in the lower atmosphere, the perfluorinated ketones have short atmospheric lifetimes and would not be expected to contribute significantly to global warming (i.e., low global warming potentials). Perfluorinated ketones which are straight chain or cyclic can be prepared as described in U.S. Pat. No. 5,466,877 (Moore et al.) which in turn can be derived from the fluorinated esters described in U.S. Pat. No. 5,399,718 (Costello et al.). Perfluorinated ketones that are branched can be prepared as described in U.S. Pat. No. 3,185,734 (Fawcett et al.). All of these patents are incorporated by reference in their entirety.
Hydrofluoroketones (HFKs) that are useful in the present invention include those ketones having only fluorine and hydrogen atoms attached to the carbon backbone. The carbon backbone can be linear, branched, or cyclic, or combinations thereof, and preferably will have about 4 to about 7 carbon atoms. Representative examples of hydrofluoroketone compounds suitable for use in the processes and compositions of this invention include: HCF2CF2C(O)CF(CF3)2, CF3C(O)CH2C(O)CF3, C2H5C(O)CF(CF3)2, CF2CF2C(O)CH3, (CF3)2CFC(O)CH3, CF3CF2C(O)CHF2, CF3CF2C(O)CH2F, CF3CF2C(O)CH2CF3, CF3CF2C(O)CH2CH3, CF3CF2C(O)CH2CHF2, CF3CF2C(O)CH2CHF2, CF3CF2C(O)CH2CH2F, CF3CF2C(O)CHFCH3, CF3CF2C(O)CHFCHF2, CF3CF2C(O)CHFCH2F, CF3CF2C(O)CF2CH3, CF3CF2C(O)CF2CHF2, CF3CF2C(O)CF2CH2F, (CF3)2CFC(O)CHF2, (CF3)2CFC(O)CH2F, CF3CF(CH2F)C(O)CHF2, CF3CF(CH2F)C(O)CH2F, and CF3CF(CH2F)C(O)CF3. Some hydrofluoroketones can be prepared by reacting a fluorinated acid with a Grignard reagent such as an alkylmagnesium bromide in an aprotic solvent, as described in Japanese Patent No. 2,869,432. For example CF2CF2C(O)CH3 can be prepared by reacting pentafluoropropionic acid with magnesium methyl bromide in dibutyl ether. Other hydrofluoroketones can be prepared by reacting a partially fluorinated acyl fluoride with hexafluoropropylene in an anhydrous environment in the presence of fluoride ion at elevated temperature, as described in U.S. patent application Ser. No. 09/619306 (herein incorporated by reference). For example, HCF2CF2C(O)CF(CF3)2 can be prepared by oxidizing tetrafluoropropanol with acidic dichromate, then reacting the resulting HC2H4COOH with benzotrichloride to form HC2H4C(O)Cl, converting the acyl chloride to the acyl fluoride by reaction with anhydrous sodium fluoride, and then reacting the HC2H4C(O)F with hexafluoropropylene under pressure.
The gaseous mixture that comprises a fluorocarbon selected from the group consisting of perfluoroketones and hydrofluoroketones further comprises a carrier gas or carrier gases. Some possible carrier gases include air, CO2, argon, nitrogen and mixtures thereof. Preferably, the carrier gas that is used with the perfluroketones is dry air.
The gaseous mixture comprises a minor amount of the fluorocarbon and a major amount of the carrier gas. Preferably, the gaseous mixture consists of less than about 1% of the fluorocarbon and the balance carrier gas. More preferably, the gaseous mixture contains less than 0.5% by volume (most preferably less that 0.1% by volume) fluorocarbon, selected from the group consisting of perfluoroketones, hydrofluoroketones and mixtures thereof.
In order to keep the protective layer on the magnesium, the gaseous mixture is continuously, or nearly continuously, fed to the surface of the magnesium. Small breaks in the thin protective layer can then be healed without the possibility of such small breaks exposing molten magnesium to the air and initiating a fire.
A cover gas composition is of low toxicity both as it is applied to the molten magnesium and as it is emitted from the process in which it is used. Cover gases comprising low toxicity hydrofluoroketones and perfluoroketones, and mixtures thereof, will be safe mixtures as applied to magnesium. However, all fluorine containing cover gas composition produce measurable amounts of hydrogen fluoride upon contact with the molten magnesium due to some level of thermal degradation and reaction with magnesium at temperatures of 650 to 750xc2x0 C. Hydrogen fluoride is corrosive and toxic and its concentration in the emitted gas should be minimized. A preferred cover gas composition will, therefore, produce minimal hydrogen fluoride. See Examples, below.
Atmospheric lifetimes and global warming potentials for several fluorocarbons used in accordance with this invention, along with compounds currently known to be useful in the protection of molten magnesium as comparative examples, are presented in TABLE 2.
The perfluoroketones and hydrofluoroketones of the invention have much lower global warming potential (GWP) than the fluorocarbons known in the art such as SF6, hydrofluorocarbons, and hydrofluoroethers. As used herein, xe2x80x9cGWPxe2x80x9d is a relative measure of the warming potential of a compound based on the structure of the compound. The GWP of a compound, as defined by the Intergovernmental Panel on Climate Change (IPCC) in 1990 and updated in Scientific Assessment of Ozone Depletion: 1998 (World Meteorological Organization, Scientific Assessment of Ozone Depletion: 1998, Global Ozone Research and Monitoring Projectxe2x80x94Report No. 44, Geneva, 1999), is calculated as the warming due to the release of 1 kilogram of a compound relative to the warming due to the release of 1 kilogram of CO2 over a specified integration time horizon (ITH).             GWP      x        ⁢          (              t        xe2x80x2            )        =                    ∫        0        ITH            ⁢                        F          x                ⁢                  C                      O            x                          ⁢                  ⅇ                                    -              t                        /                          τ              x                                      ⁢                  xe2x80x83                ⁢                  ⅆ          t                                    ∫        0        ITH            ⁢                        F                      CO            2                          ⁢                              C                          CO              2                                ⁢                      (            t            )                          ⁢                  xe2x80x83                ⁢                  ⅆ          t                    
where F is the radiative forcing per unit mass of a compound (the change in the flux of radiation through the atmosphere due to the IR absorbance of that compound), C is the atmospheric concentration of a compound, xcfx84 is the atmospheric lifetime of a compound, t is time and x is the compound of interest.
The commonly accepted ITH is 100 years representing a compromise between short-term effects (20 years) and longer-term effects (500 years or longer). The concentration of an organic compound, x, in the atmosphere is assumed to follow pseudo first order kinetics (i.e., exponential decay). The concentration of CO2 over that same time interval incorporates a more complex model for the exchange and removal of CO2 from the atmosphere (the Bern carbon cycle model).
Carbonyl compounds such as aldehydes and ketones have been shown to have measurable photolysis rates in the lower atmosphere resulting in very short atmospheric lifetimes. Compounds such as formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde, acetone, 2-butanone, 2-pentanone and 3-pentanone have atmospheric lifetimes by photolysis ranging from 4 hours to 38 days (Martinez, R. D., et al., 1992, Atmospheric Environment, 26, 785-792, and Seinfeld, J. H. and Pandis, S. N., Atmospheric Chemistry and Physics, John Wiley and Sons, New York, p. 288, 1998). CF3CF2C(O)CF(CF3)2 has an atmospheric lifetime of approximately 5 days based on photolysis studies at 300 nm. Other perfluoroketones and hydrofluoroketones show similar absorbances near 300 nm and are expected to have similar atmospheric lifetimes.
The very short lifetimes of the perfluoroketones and hydrofluoroketones lead to very low GWPs. A measured IR cross-section was used to calculate the radiative forcing value for CF3CF2C(O)CF(CF3)2 using the method of Pinnock, et al. (J. Geophys. Res., 100, 23227, 1995). Using this radiative forcing value and the 5-day atmospheric lifetime the GWP (100 year ITH) for CF3CF2C(O)CF(CF3)2 is 1. Assuming a maximum atmospheric lifetime of 38 days and infrared absorbance similar to that of CF3CF2C(O)CF(CF3)2 the GWP for HCF2CF2C(O)CF(CF3)2 is calculated to be 9. The perfluoroketones and hydrofluoroketones of the invention typically have a GWP less than about 10.
As a result of their rapid degradation in the lower atmosphere, the perfluoroketones and hydrofluoroketones have short lifetimes and would not be expected to contribute significantly to global warming. The low GWP of the perfluoroketones make them well suited for use as an environmentally preferred cover gas.
Also, the PFKs and HFKs of this invention can react more fully with molten magnesium than does SF6. As a result less unreacted cover gas can be emitted to the atmosphere; less cover gas can be required to produce a comparably performing protective film; or both. Consequently, useful concentrations of the cover gas can be lowered, thus reducing the global warming impact. The full substitution of fluorocarbons of the present invention for SF6 can be accomplished without increasing the risk to worker safety since these materials (PFKs, and HFKs) are of low toxicity, are non-flammable, and are generally very innocuous materials.
Substitution for SF6 with a PFK, or HFK, alone or as a mixture thereof, can provide protection of molten magnesium in various processes, such as magnesium refining, alloying, formation of ingots or casting of parts. This substitution can be straightforward and can provide the same utility as a reactive cover gas that only SF6 does currently. Surface films produced with the fluorocarbons of the present invention can be more stable to higher temperatures than those formed with SO2, enabling work with higher melt temperatures (e.g., additional alloys, more complex casting parts). Improvements realized through the use of fluorocarbons of the present invention as reactive cover gases can include a significant reduction in the emission of a potent greenhouse gas (i.e., SF6), a potential reduction in the amount of fluorine-containing reactive cover gas required to provide protection, and a reduction in total emissions. This substitution can be done without increasing risks for workers since the fluorocarbons of the present invention are all safe materials with which to work, have low toxicity, are nonflammable, and are not a detriment to production equipment.
The use of perfluoroketones, or hydrofluoroketones, or mixtures thereof, in a gaseous mixture demonstrate the ability to also put out fires that are already occurring on the surface of molten magnesium. Therefore, the gases also may be used to extinguish fires on molten magnesium.